CN112624212A - Carbon-doped nickel hydroxide cobalt manganese material and preparation method thereof - Google Patents
Carbon-doped nickel hydroxide cobalt manganese material and preparation method thereof Download PDFInfo
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- CN112624212A CN112624212A CN202011511510.7A CN202011511510A CN112624212A CN 112624212 A CN112624212 A CN 112624212A CN 202011511510 A CN202011511510 A CN 202011511510A CN 112624212 A CN112624212 A CN 112624212A
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- 239000000463 material Substances 0.000 title claims abstract description 35
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical compound [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 59
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 59
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 44
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011572 manganese Substances 0.000 claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims abstract description 5
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 45
- 229940053662 nickel sulfate Drugs 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 38
- 229940044175 cobalt sulfate Drugs 0.000 claims description 35
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 35
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 35
- 229940099596 manganese sulfate Drugs 0.000 claims description 35
- 239000011702 manganese sulphate Substances 0.000 claims description 35
- 235000007079 manganese sulphate Nutrition 0.000 claims description 35
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011268 mixed slurry Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 claims description 5
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000012432 intermediate storage Methods 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- -1 ammonia nitrogen ions Chemical class 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910006669 Li1+xMn2−yMyO4 Inorganic materials 0.000 description 1
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a carbon-doped nickel hydroxide cobalt manganese material and a preparation method thereof, wherein the carbon-doped nickel hydroxide cobalt manganese material has a chemical general formula: nixCoyMn1‑x‑y（OH）2Wherein x/y is more than or equal to 0.1 and less than or equal to 0.6. The carbon-doped nickel, cobalt and manganese hydroxide precursor is prepared by taking sodium hydroxide, ammonia water, nickel sulfate, cobalt and manganese as raw materials and adopting a coprecipitation reaction.
Description
The technical field is as follows:
the invention belongs to the field of preparation of lithium battery anode materials, and particularly relates to a carbon-doped nickel hydroxide cobalt manganese hydroxide material and a preparation method thereof.
Background art:
the lithium ion battery is used as a novel green secondary battery, is used as a new generation of rechargeable high-energy battery, is widely applied to various aspects such as wireless communication, transportation, aerospace and the like, and is one of main factors influencing the cost and the performance of the lithium ion battery. The lithium ion anode material is a crucial factor for restricting the performance of the lithium ion battery in all aspects.
There are many series of currently developed positive electrode materials for lithium ion batteries, mainly including layered lithium cobalt oxide series, layered lithium nickel oxide series, spinel-type lithium manganese oxide series, and olivine-type lithium iron phosphate series. Among the cathode materials, LiCoO2 has been widely used as a lithium ion secondary battery commercialized cathode material because of its excellent electrochemical properties, but since Co in LiCoO2 is a scarce resource, it is expensive, it is easy to pollute the environment, and the safety of LiCoO2 is poor, it limits the application of a lithium ion secondary battery using LiCoO2 as a cathode material in hybrid electric vehicles and pure electric vehicles. The current power batteries are mainly ternary material battery systems and lithium iron phosphate battery systems.
With the increasing requirements on the material and power performance of power batteries, the lithium-rich manganese-based positive electrode material has a wide development prospect, particularly, the research on the high-voltage lithium-rich manganese-based positive electrode material is more and more common, and the development of a high-performance lithium-rich manganese-based positive electrode material product requires the development of a high-quality nickel-manganese ternary precursor material as a precursor of the lithium-rich manganese-based positive electrode material.
Therefore, in order to improve the problems in the use of the lithium ion battery or improve the performance of the lithium ion battery, how to prepare the positive electrode material with reliable quality has great correlation with the performance of the precursor, and the nickel, cobalt and manganese hydroxide precursor material with stable and reliable performance can prepare the lithium-rich manganese-based positive electrode material with excellent performance, so that the performance of the positive electrode material of the lithium battery is ensured.
The invention content is as follows:
the invention provides a carbon-doped nickel hydroxide cobalt manganese material and a preparation method thereof, wherein sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese are used as raw materials, a carbon-doped nickel hydroxide cobalt manganese precursor is prepared by coprecipitation reaction, and a carbon source is added in the preparation process.
The invention discloses a carbon-doped nickel, cobalt and manganese hydroxide material, which has a chemical general formula: nixCoyMn1-x-y(OH)2Wherein x/y is more than or equal to 0.1 and less than or equal to 0.6.
The carbon-doped nickel cobalt manganese hydroxide material provided by the invention preferably has a chemical formula of Ni0.6Co0.1Mn0.3(OH)2Or Ni0.5Co0.2Mn0.3(OH)2Or Ni0.6Co0.2Mn0.2(OH)2。
The invention also aims to provide a preparation method of the carbon-doped nickel hydroxide cobalt manganese material, which takes sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese as raw materials and comprises the following steps:
1) preparing a reaction solution, namely preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed solution with a certain substance quantity concentration according to a proportion, and preparing sodium hydroxide and ammonia water into a mixed solution with a corresponding substance quantity concentration according to a proportion;
2) performing coprecipitation reaction, namely continuously pumping the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water into a reaction device through a precision metering pump according to a certain flow ratio, and performing chemical reaction under the conditions of continuous stirring and heating to obtain mixed slurry of nickel, cobalt and manganese hydroxide;
3) in the process of the step 2), adding a carbon source into the reaction device according to the feeding amount of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water in proportion to form composite slurry, and then aging for 12-15 h;
4) filtering, washing, dehydrating and filter-pressing the composite slurry obtained in the step 3) to form a filter cake, and drying to obtain the carbon-doped nickel, cobalt and manganese hydroxide product.
The preparation method of the carbon-doped nickel hydroxide cobalt manganese material comprises the step 1) of mixing the nickel sulfate, the cobalt sulfate and the manganese sulfate solution at a concentration of 2.0-5.0mol/L, and mixing the sodium hydroxide and the ammonia water at a concentration of 1.0-3.0 mol/L.
The preparation method of the carbon-doped nickel hydroxide cobalt manganese material comprises the following steps of 2) controlling the adding flow of nickel sulfate, a mixed solution of cobalt sulfate and manganese sulfate and a mixed solution of sodium hydroxide and ammonia water into a reaction device to be 80-100L/h; controlling the stirring speed of the reaction device to be 100-300 r/min; the reaction temperature is controlled to be 40-60 ℃.
In the preparation method of the carbon-doped nickel hydroxide cobalt manganese material, the carbon source in the step 3) can be conductive carbon black, and can also be graphene or graphite, and the adding amount of the carbon source is 0.5-5.0 wt%.
The preparation method of the carbon-doped nickel hydroxide cobalt manganese material comprises the step 4) of filtering the carbon-doped nickel hydroxide cobalt manganese hydroxide mixed slurry obtained in the step 3) through a plate frame to obtain carbon-doped nickel hydroxide cobalt manganese filter residue, washing the carbon-doped nickel hydroxide cobalt manganese filter residue for a plurality of times by using a dilute ammonia solution, then washing the carbon-doped nickel hydroxide cobalt manganese filter residue by using deionized water to remove impurities to obtain high-purity carbon-doped nickel hydroxide cobalt manganese, dehydrating the carbon-doped nickel hydroxide cobalt manganese to form a carbon-doped nickel hydroxide cobalt manganese filter cake, and drying the carbon-doped nickel hydroxide cobalt manganese filter cake by using a drying device to obtain a carbon-doped nickel hydroxide cobalt manganese product; and diluted alkali water solution can be used for washing, and the concentration of the diluted ammonia water solution is controlled to be 0.2-0.3 mol/L.
The drying is vacuum drying or spray drying, the drying temperature is controlled to be 80-90 ℃, the drying time is 25-30h, and the crystal water is not decomposed, so that the carbon-doped nickel, cobalt and manganese hydroxide product is obtained.
The invention relates to a preparation method of a carbon-doped nickel hydroxide cobalt manganese material, which mainly comprises the following process steps: preparing a nickel-cobalt-manganese acid solution → preparing sodium hydroxide and an ammonia solution → preparing nickel sulfate, cobalt, manganese solution and sodium hydroxide and ammonia solution → simultaneously dripping into a reaction device → coprecipitation reaction → adding a carbon source in the reaction process → carbon-doped nickel-cobalt-manganese hydroxide mixed slurry → pressure filtration cleaning → detection → drying → carbon-doped nickel-cobalt-manganese hydroxide products.
The chemical formula of the carbon-doped nickel hydroxide, cobalt and manganese hydroxide prepared by the method is NixCoyMn1-x-y(OH)2Wherein x/y is not less than 0.1Less than or equal to 0.6. The product is detected by related departments, and each technical index is as follows, and the product is shown in the table 1 to be Ni in chemical formula0.6Co0.1Mn0.3(OH)2The technical parameters of the method, the product storage and transportation conditions, shade, dryness, moisture resistance and moisture resistance.
TABLE 1
The lithium-rich manganese-based positive electrode material fired by the carbon-doped nickel, cobalt and manganese hydroxide has excellent safety performance, high-temperature performance and cycle life; the prepared lithium ion battery has excellent charge and discharge performance and cycle performance.
Description of the drawings:
FIG. 1 is an SEM image of a carbon-doped nickel cobalt manganese hydroxide product prepared by the invention;
fig. 2 is a time-voltage-current diagram of the lithium-rich manganese-based anode material fired by the carbon-doped nickel cobalt manganese hydroxide prepared by the invention.
The specific implementation mode is as follows:
the invention is described in further detail below with reference to specific embodiments, it being understood that the foregoing general description and the following detailed description of the invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. The components described in the examples of the present invention are commercially available.
The invention discloses a carbon-doped nickel, cobalt and manganese hydroxide material, which has a chemical general formula: nixCoyMn1-x-y(OH)2Wherein x/y is more than or equal to 0.1 and less than or equal to 0.6.
Further preferred of said formula is Ni0.6Co0.1Mn0.3(OH)2Or Ni0.5Co0.2Mn0.3(OH)2Or Ni0.6Co0.2Mn0.2(OH)2。
The invention relates to a preparation method of a carbon-doped nickel hydroxide cobalt manganese material, which takes sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese as raw materials and comprises the following steps:
1) preparing a reaction solution, namely preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed solution with a certain substance quantity concentration according to a proportion, and preparing sodium hydroxide and ammonia water into a mixed solution with a corresponding substance quantity concentration according to a proportion; preferably, the concentration of the prepared sodium hydroxide and ammonia water solution is controlled to be 1.0-3.0 mol/L; the concentration of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate is 2.0-5.0 mol/L;
2) performing coprecipitation reaction, namely continuously pumping the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water into a reaction device through a precision metering pump according to a certain flow ratio, and performing chemical reaction under the conditions of continuous stirring and heating to obtain mixed slurry of nickel, cobalt and manganese hydroxide; controlling the adding flow rate of adding the nickel sulfate, the mixed solution of cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water into the reaction device to be 80-100L/h; controlling the stirring speed of the reaction device to be 100-300 r/min; controlling the reaction temperature to be 40-60 ℃;
3) in the process of the step 2), adding a carbon source into the reaction device according to the feeding amount of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water in proportion to form composite slurry, and then aging for 12-15 h; the carbon source can be conductive carbon black, and can also be graphene or graphite, and the adding amount of the carbon source is 0.5-5.0 wt%;
4) filtering, washing, dehydrating and filter-pressing the composite slurry obtained in the step 3) to form a filter cake, and drying to obtain the carbon-doped nickel, cobalt and manganese hydroxide product of the lithium-manganese-based anode material. Filtering the carbon-doped nickel cobalt manganese hydroxide mixed slurry obtained in the step 3) by using a plate frame to obtain carbon-doped nickel cobalt manganese hydroxide filter residues, washing the filter residues for a plurality of times by using a dilute ammonia solution, then washing the filter residues by using deionized water to remove impurities to obtain high-purity carbon-doped nickel cobalt manganese hydroxide, dehydrating the high-purity carbon-doped nickel cobalt manganese hydroxide to form a carbon-doped nickel cobalt manganese hydroxide filter cake, and drying the carbon-doped nickel cobalt manganese hydroxide filter cake by using a drying device; the drying is vacuum drying or spray drying, the drying temperature is controlled to be 80-90 ℃, the drying time is 25-30 hours, and the crystal water in the precursor is not decomposed, so that the carbon-doped nickel cobalt manganese hydroxide product is obtained.
Example 1
The method for preparing carbon-doped nickel hydroxide cobalt manganese material in this example 1 refers to Ni0.6Co0.1Mn0.3(OH)2The preparation method of (1).
The invention relates to a carbon-doped nickel hydroxide cobalt manganese material, namely Ni0.6Co0.1Mn0.3(OH)2The preparation method takes sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese as raw materials, and comprises the following steps:
preparing raw materials, namely sending the nickel sulfate, cobalt sulfate, manganese sulfate raw materials and the like which are purchased from the market and used for reaction into a raw material warehouse for storage, respectively conveying the raw materials into a nickel sulfate, cobalt sulfate and manganese sulfate bin reaction device of a raw material workshop according to the required amount, weighing by electronic decrement, mixing the raw materials into a dissolving tank according to the mass ratio, adding a fixed amount of pure water for dissolving, and sending the raw materials into an intermediate storage tank. The sodium hydroxide is purchased from the market and then sent to a raw material warehouse for storage, and is proportionally mixed into a dissolving tank by an electronic decrement scale and dissolved by quantitative pure water, and then is sent to an intermediate storage tank for standby. The ammonia water is purchased from the market and sent into an ammonia water tank for storage. According to the required quantity, the purchased ammonia water is prepared into ammonia water with specified concentration, and the ammonia water is sent into an intermediate storage tank for standby.
1) Preparing a reaction solution, namely preparing a sodium hydroxide and ammonia water mixed solution with the amount concentration of 1.5mol/L by using pure water according to the proportion of the sodium hydroxide and the ammonia water, and preparing nickel sulfate, cobalt sulfate and manganese sulfate into a nickel sulfate, cobalt sulfate and manganese sulfate mixed solution with the amount concentration of 3.0mol/L of corresponding substances according to the proportion of the nickel sulfate, cobalt sulfate and manganese sulfate;
2) performing coprecipitation reaction, namely adding a mixed solution of sodium hydroxide and ammonia water with the concentration of 1.5mol/L and a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the concentrations of 3.0mol/L into a reaction device respectively and simultaneously, performing chemical reaction under the conditions of continuous stirring and heating, and controlling the stirring speed of the reaction device to be 240 r/min; controlling the temperature of the coprecipitation reaction to be about 55 ℃ to obtain nickel cobalt manganese hydroxide mixed slurry;
3) adding 2.0 wt% of conductive carbon black into the reaction device in the process of the step 2) to form a composite of the nickel hydroxide, cobalt and manganese mixed slurry and the conductive carbon black, and then aging for 13 h;
4) filtering the mixed slurry of the nickel cobalt manganese hydroxide and the conductive carbon black obtained in the step 3) by a plate frame to obtain carbon-doped nickel cobalt manganese hydroxide filter residue, washing the filter residue for a plurality of times by using a dilute ammonia water solution with the concentration of 0.2-0.3mol/L, washing the filter residue by using dilute ammonia water, washing the filter residue by using deionized water to remove impurities to obtain high-purity carbon-doped nickel cobalt manganese hydroxide, sending washing waste liquid to a sewage treatment station, removing ammonia nitrogen ions by using an ammonia evaporation method, sending the washing waste liquid to a sewage treatment plant for treatment and discharge after reaching the standard; dehydrating the high-purity carbon-doped nickel cobalt manganese hydroxide to form a carbon-doped nickel cobalt manganese hydroxide filter cake, and drying the carbon-doped nickel cobalt manganese hydroxide filter cake by using a drying device; and the drying is vacuum drying or spray drying, the drying temperature is controlled to be 80 ℃, and the drying time is 25 hours, so that the carbon-doped nickel, cobalt and manganese hydroxide product is obtained.
The specification requirements of the raw materials required by the invention are as follows: nickel sulfate, cobalt sulfate and manganese sulfate are all battery grade; sodium hydroxide technical grade; ammonia industrial grade.
Example 2
The method for preparing carbon-doped nickel hydroxide cobalt manganese material in this example 2 refers to Ni0.5Co0.2Mn0.3(OH)2The preparation method of (1).
The invention relates to a carbon-doped nickel hydroxide cobalt manganese material, namely Ni0.5Co0.2Mn0.3(OH)2The preparation method takes sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese as raw materials, and comprises the following steps:
preparing raw materials, namely sending the nickel sulfate, cobalt sulfate, manganese sulfate raw materials and the like which are purchased from the market and used for reaction into a raw material warehouse for storage, respectively conveying the raw materials into a nickel sulfate, cobalt sulfate and manganese sulfate bin reaction device of a raw material workshop according to the required amount, weighing by electronic decrement, mixing the raw materials into a dissolving tank according to the mass ratio, adding a fixed amount of pure water for dissolving, and sending the raw materials into an intermediate storage tank. The sodium hydroxide is purchased from the market and then sent to a raw material warehouse for storage, and is proportionally mixed into a dissolving tank by an electronic decrement scale and dissolved by quantitative pure water, and then is sent to an intermediate storage tank for standby. The ammonia water is purchased from the market and sent into an ammonia water tank for storage. According to the required quantity, the purchased ammonia water is prepared into ammonia water with specified concentration, and the ammonia water is sent into an intermediate storage tank for standby.
1) Preparing a reaction solution, namely preparing sodium hydroxide solution with the quantity concentration of 2.0mol/L from sodium hydroxide and ammonia water by pure water according to a proportion, and preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the quantity concentration of 3.5mol/L of corresponding substances by water according to a proportion;
2) performing coprecipitation reaction, namely respectively and simultaneously adding a mixed solution of sodium hydroxide and ammonia water with the concentration of 2.0mol/L and a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the concentrations of 3.5mol/L into a reaction device, performing chemical reaction under the conditions of continuous stirring and heating, and simultaneously controlling the stirring speed of the reaction device to be 260 r/min; controlling the coprecipitation reaction temperature to be about 55 ℃ to obtain nickel-cobalt-manganese hydroxide mixed slurry of the lithium-rich manganese-based positive electrode material;
3) adding 2.5 wt% of conductive carbon black into the reaction device in the process of the step 2) to form a composite of the nickel hydroxide, cobalt and manganese hydroxide mixed slurry and the conductive carbon black, and then aging for 13 h;
4) filtering the mixed slurry of the nickel cobalt manganese hydroxide and the conductive carbon black obtained in the step 3) by a plate frame to obtain carbon-doped nickel cobalt manganese hydroxide filter residue, washing the filter residue for a plurality of times by using a dilute ammonia water solution with the concentration of 0.3mol/L, washing the filter residue by using dilute ammonia water, washing the filter residue by using deionized water for a plurality of times to remove impurities to obtain high-purity carbon-doped nickel cobalt manganese hydroxide, sending washing waste liquid to a sewage treatment station, removing ammonia nitrogen ions by using an ammonia evaporation method, sending the washing waste liquid to a sewage treatment plant for treatment and discharge after reaching the standard; dehydrating the high-purity carbon-doped nickel cobalt manganese hydroxide to form a carbon-doped nickel cobalt manganese hydroxide filter cake, and drying the carbon-doped nickel cobalt manganese hydroxide filter cake by using a drying device; the drying is spray drying, the drying temperature is controlled to be 90 ℃, and the drying time is 25 hours, so that the carbon-doped nickel, cobalt and manganese hydroxide product is obtained.
The specification requirements of the raw materials required by the invention are as follows: nickel sulfate, cobalt sulfate and manganese sulfate are all battery grade; sodium hydroxide technical grade; ammonia industrial grade.
Example 3
The method for preparing carbon-doped nickel hydroxide cobalt manganese material in this embodiment 3 refers to Ni0.6Co0.2Mn0.2(OH)2The preparation method of (1).
The invention relates to a carbon-doped nickel hydroxide cobalt manganese material, namely Ni0.6Co0.2Mn0.2(OH)2The preparation method takes sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese as raw materials, and comprises the following steps:
preparing raw materials, namely sending the nickel sulfate, cobalt sulfate, manganese sulfate raw materials and the like which are purchased from the market and used for reaction into a raw material warehouse for storage, respectively conveying the raw materials into a nickel sulfate, cobalt sulfate and manganese sulfate bin reaction device of a raw material workshop according to the required amount, weighing by electronic decrement, mixing the raw materials into a dissolving tank according to the mass ratio, adding a fixed amount of pure water for dissolving, and sending the raw materials into an intermediate storage tank. The sodium hydroxide is purchased from the market and then sent to a raw material warehouse for storage, and is proportionally mixed into a dissolving tank by an electronic decrement scale and dissolved by quantitative pure water, and then is sent to an intermediate storage tank for standby. The ammonia water is purchased from the market and sent into an ammonia water tank for storage. According to the required quantity, the purchased ammonia water is prepared into ammonia water with specified concentration, and the ammonia water is sent into an intermediate storage tank for standby.
1) Preparing a reaction solution, namely preparing a sodium hydroxide and ammonia water mixed solution with the amount concentration of 1.5mol/L by using pure water according to the proportion of the sodium hydroxide and the ammonia water, and preparing nickel sulfate, cobalt sulfate and manganese sulfate into a nickel sulfate, cobalt sulfate and manganese sulfate mixed solution with the amount concentration of 3.5mol/L of corresponding substances according to the proportion of the nickel sulfate, cobalt sulfate and manganese sulfate;
2) performing coprecipitation reaction, namely adding a mixed solution of sodium hydroxide and ammonia water with the concentration of 1.5mol/L and a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the concentrations of 3.5mol/L into a reaction device respectively and simultaneously, performing chemical reaction under the conditions of continuous stirring and heating, and controlling the stirring speed of the reaction device to be 250 r/min; controlling the coprecipitation reaction temperature to be about 50 ℃ to obtain nickel-cobalt-manganese hydroxide mixed slurry of a precursor of the lithium-rich manganese-based positive electrode material;
3) adding 1.5 wt% of conductive carbon black into the reaction device in the process of the step 2) to form a composite of the nickel hydroxide, cobalt and manganese hydroxide mixed slurry and the conductive carbon black, and then aging for 12 h;
4) filtering the mixed slurry of the nickel cobalt manganese hydroxide and the conductive carbon black obtained in the step 3) by a plate frame to obtain carbon-doped nickel cobalt manganese hydroxide filter residue, washing the filter residue for a plurality of times by using a dilute ammonia water solution with the concentration of 0.3mol/L, washing the filter residue by using dilute ammonia water, washing the filter residue by using deionized water for a plurality of times to remove impurities to obtain high-purity carbon-doped nickel cobalt manganese hydroxide, sending washing waste liquid to a sewage treatment station, removing ammonia nitrogen ions by using an ammonia evaporation method, sending the washing waste liquid to a sewage treatment plant for treatment and discharge after reaching the standard; dehydrating the high-purity carbon-doped nickel cobalt manganese hydroxide to form a carbon-doped nickel cobalt manganese hydroxide filter cake, and drying the carbon-doped nickel cobalt manganese hydroxide filter cake by using a drying device; the drying is spray drying, the drying temperature is controlled to be 80 ℃, and the drying time is 30 hours, so that the carbon-doped nickel, cobalt and manganese hydroxide product is obtained.
The specification requirements of the raw materials required by the invention are as follows: nickel sulfate, cobalt sulfate and manganese sulfate are all battery grade; sodium hydroxide technical grade; ammonia industrial grade.
Comparative examples
A preparation method of a manganese-based anode material precursor material according to the existing raw materials; the comparative example is a manganese-based anode material precursor, such as the preparation of a trimanganese tetroxide precursor, such as lithium manganese with a chemical formula of Li1+ xMn2-yMyO4, and the raw material is manganese acetate, and the like, nickel salt, manganese acetate and the like which are purchased from the market and used for reaction are sent to a raw material warehouse for storage, are respectively sent to a nickel and manganese acetate bin reaction device of a raw material workshop according to the required quantity, are weighed by electronic decrement, are matched into a dissolving tank according to the mass proportion, are dissolved by adding quantitative pure water, and are sent to an intermediate storage tank. The alkaline water is purchased from the market and sent into a tank for storage. The required amount is sent into an intermediate storage tank for standby.
Placing manganese source solution, impurity-permeating element M and precipitator in a reaction device by adopting an air oxidation liquid-phase precipitation process method, carrying out mixing reaction, and controlling the corresponding reaction temperature to be about 70 ℃; complexing agent, dispersant and surfactant such as PVP and the like are added to prepare trimanganese tetroxide precursor; the preparation process is complex and can not meet the technical requirements of the invention.
Claims (8)
1. A carbon-doped nickel cobalt manganese hydroxide material has a chemical formula: nixCoyMn1-x-y（OH）2Wherein x/y is more than or equal to 0.1 and less than or equal to 0.6.
2. The carbon-doped nickel cobalt manganese hydroxide material as claimed in claim 1, wherein the chemical formula is Ni0.6Co0.1Mn0.3（OH）2Or Ni0.5Co0.2Mn0.3（OH）2Or Ni0.6Co0.2Mn0.2（OH）2。
3. The preparation method of the carbon-doped nickel hydroxide cobalt manganese material according to claim 1 or 2, which takes sodium hydroxide, ammonia water and nickel sulfate, cobalt and manganese as raw materials, and is characterized by comprising the following method steps:
1) preparing a reaction solution,
preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed solution with a certain substance quantity concentration according to a proportion, and preparing sodium hydroxide and ammonia water into a mixed solution with a corresponding substance quantity concentration according to a proportion;
2) the co-precipitation reaction is carried out,
continuously pumping the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water into a reaction device through a precision metering pump according to a certain flow ratio, and carrying out chemical reaction under the conditions of continuous stirring and heating to obtain mixed slurry of nickel, cobalt and manganese hydroxide;
3) in the process of the step 2), adding a carbon source into the reaction device according to the feeding amount of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate and the mixed solution of sodium hydroxide and ammonia water in proportion to form composite slurry, and then aging for 12-15 h;
4) filtering, washing, dehydrating and filter-pressing the mixed slurry of the nickel, cobalt and manganese hydroxide obtained in the step 3) to form a filter cake, and drying to obtain a precursor nickel, cobalt and manganese hydroxide product of the lithium-rich manganese-based cathode material.
4. The method for preparing the carbon-doped nickel hydroxide, cobalt and manganese material as claimed in claim 3, wherein the concentration of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate in step 1) is 2.0-5.0mol/L, and the concentration of the mixed solution of sodium hydroxide and ammonia water is 1.0-3.0 mol/L.
5. The method for preparing the carbon-doped nickel hydroxide, cobalt hydroxide and manganese material according to claim 3, wherein in the step 2), the adding flow rate of the nickel sulfate, the mixed solution of cobalt sulfate and manganese sulfate, and the mixed solution of sodium hydroxide and ammonia water into the reaction device is controlled to be 80-100L/h; controlling the stirring speed of the reaction device to be 100-300 r/min; the reaction temperature is controlled to be 40-60 ℃.
6. The method for preparing the carbon-doped nickel hydroxide, cobalt and manganese hydroxide material according to claim 3, wherein the carbon source in the step 3) can be conductive carbon black, graphene or graphite, and the addition amount of the carbon source is 0.5-5.0 wt%.
7. The method for preparing the carbon-doped nickel cobalt manganese hydroxide material according to claim 3, wherein the step 4) is that the carbon-doped nickel cobalt manganese hydroxide mixed slurry obtained in the step 3) is filtered by a plate frame to obtain carbon-doped nickel cobalt manganese hydroxide filter residue, the filter residue is washed for a plurality of times by using a dilute ammonia solution, and then the impurities are removed by washing with deionized water to obtain high-purity carbon-doped nickel cobalt manganese hydroxide, the carbon-doped nickel cobalt manganese hydroxide is dehydrated to form a carbon-doped nickel cobalt manganese hydroxide filter cake, and the carbon-doped nickel cobalt manganese hydroxide filter cake is dried by a drying device to obtain a carbon-doped nickel cobalt manganese hydroxide product; and diluted alkali water solution can be used for washing, and the concentration of the diluted ammonia water solution is controlled to be 0.2-0.3 mol/L.
8. The method for preparing the carbon-doped nickel hydroxide, cobalt and manganese hydroxide material according to claim 3, wherein the drying is vacuum drying or spray drying, the drying temperature is controlled to be 80-90 ℃, the drying time is 25-30h, and the crystal water is not decomposed, so that the carbon-doped nickel hydroxide, cobalt and manganese hydroxide product is obtained.
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